Dye compositions

ABSTRACT

A fluorinated organic acid compound of the formula

United States Patent [191 Uffner Feb. 20, 1973 [541 DYE COMPOSITIONS [751 Inventor: Melville W. Uffner, Media, Pa.

[73] Assignee: Air Products and Chemicals, Inc.,

Philadelphia, Pa.

[22] Filed: Aug. 19, 1970 [21] Appl. No.: 65,312

[52] U.S. Cl. ..l06/209, 8/65, 117/1355, 117/1395 C, 260/296 F [51] Int. Cl. ..C08b 25/00 [58] Field of Search ..l06/l62, 209; 260/296 F; 8/65;117/139.5 C, 135.5; 165/313 [56] References Cited UNITED STATES PATENTS 3,576,019 4/1971 Sweeney ..260/404.5

3,282,717 11/1966 Kelley ..106/205 3,414,368 3/1968 Kitamul'a 3,238,235 1/1966 Hauptschein ..260/29.6 F

Primary Examiner-Theodore Morris Att0rneyB. Max Klevit and David T. Nikaido [57] ABSTRACT A fluorinated organic acid compound of the formula C F CoNRCl-lRCooH,

13 Claims, No Drawings DYE coMPosmoNs BACKGROUND OF THE INVENTION The present invention relates to compositions for dyeing textiles with insoluble pigments and more particularly, to the preparation of improved pad dyeing compositions obtained by the incorporation of certain fluorinated organic acid compounds with a dispersion containing a pigment, a bonding agent and a dispersing agent.

conventionally, pigment dyeing systems consist of a dispersion of finely ground pigment and binder compound. One method of pad dyeing is to immerse the textile in a bath containing the pigment and binder compound and then pass the textile between squeeze rolls which remove the excess of color and other bath constituents. As an alternative method, one of the squeeze rolls is partially immersed in the color bath, whereby some of the bath is carried to the nip between the partially immersed roll and the roll adjacent to it. In the latter case, the textile is dyed by passing between the rolls without previous immersion in the bath. The amount of pigment in respect to the amount of resin binder employed will vary with the character of pigment and the depth of color desired. Properly applied, the pigment should impinge on the fabric surface with a minimum of excess binder resin protecting the surface. The process of pad dyeing with pigments has had serious drawbacks. One of these drawbacks is the fact that the pigment dyed textile may have what is described as poor appearance. In other words, the dyeing is uneven, showing dark areas and light areas in the textile material. This unevenness may be due to the migration of the pigment. Another drawback is the fact that the pigment dyed textile material does not have durability to dry cleaning and laundering.

Although fluorochemicals have been used to impart soil repellency characteristics to textiles and are in fact 'used commercially today for that purpose, it was unexpected to find that certain fluorochemicals can be incorporated into dye compositions to improve the uniformity of fabric dyeing and to impart durability to the dye applied to the fabrics.

SUMMARY OF THE INVENTION An object of the present invention is to provide improved pad dyeing compositions and a method of preparing the same.

Another object of the present invention is to provide dye compositions, comprising certain fluorinated organic acid compounds and a dispersion containing a pigment, bonding agent and dispersing agent, which provide uniformity of fabric dyeing and impart durability to the dye applied to the fabric.

Still another object of the present invention is to provide pad dyeing compositions having improved uniformity of fabric dyeing together with soil repellency and soil release characteristics.

These and other objects, advantages and features of the invention are obtained by the addition of 0.1 to 5 percent by weight of a fluorinated organic acid compound having the formula wherein each R is independently selected from H or an alkyl radical of one to eight carbon atoms, and n is an integer of 6 to 18, to a dispersion containing a pigment, bonding agent and a dispersing agent. The resulting dye compositions not only permit fabrics to be dyed more uniformly, but impart durability to the dye applied to the fabric, such that the dye is more durable to more laundering. The dyeing compositions of the present invention also render the dyed fabric soil repellent.

DESCRIFI'ION OF THE PREFERRED EMBODIMENTS In a preferred embodiment of the invention, bonding agent is added to a dispersion of pigment and the total material is stirred until homogeneous. The dispersing agent, preferably sodium alginate, is then added to the homogeneous material. For maximum pad bath stability, the bath is then adjusted to a pl-I equal to or greater than 8 by the addition of a base. Finally, the fluorinated organic acid compound is added to the aqueous dispersion and the resulting mixture is stirred until the composition is homogeneous. The resulting composition constitutes the bath which is used for padding fabric. Typically, the fabric is weighed before and after padding, and the pressure on the padding rolls is adjusted to yield the desired wet pickup of the composition.

The fluorinated organic acid compounds employed in this invention have the structure C F CONRCHRCOOH wherein each R is independently selected from H or an alkyl radical of one to eight carbon atoms and n is an integer of 6 to 18. Representative compounds include perfluorohexanoylamino acetic acid, perfluorooctanoylamino acetic acid, perfluoroundecanoylamino acetic acid, perfluoropentadecanoylamino acetic acid, perfluorooctadecanoyl amino acetic acid, perfluoroheptanoyl-Z-amino propionic acid, perfluorooctanoyl-2-amino butyric acid and perfluoroundecanoyl- 2-aminobutyric acid, perfluorooctanoyl sarcosine and perfluoroundecanoyl-Z-amino caprylic acid. These fluorinated organic acid compounds are synthesized from organic fluorine compounds prepared by either telomerization or electrolytic fluorination.

All commercially available organic and inorganic pigments may be employed in the present invention. Such pigments include such natural organic pigments as fustic and tumeric; such synthetic organic pigments as indanthrene blues, naphthol yellows, azo reds and phthalocyanine greens; such natural inorganic pigments as umber, and ochre; and such synthetic inorganic pigments as iron blues, chrome orange, cadmium reds, zinc whites, iron oxide brown and the like. Advantageously, the pigments employed will be inert with respect to the balance of the dye composition and be fast to light. In addition, the pigments should be nonbleeding, and unaffected by cleaning solutions and soaps. Based on the active weight to be deposited on the fabric, the amount of pigment employed can vary between 0.1 to 15 percent by weight of the fabric weight, with 2 to 10 percent being a preferred amount.

For printing and dyeing of textiles, the usual procedure is to disperse the pigment particles in a liquid. An aqueous dispersion is preferred, but'various non-aqueous systems, including alcohols, ketones, etc., can be employed.

The bonding agent utilized in the present invention can include any of the bonding agents normally employed in the art, such as urea formaldehyde, melamine formaldehyde, ethyl cellulose, mixtures of ethyl and butyl cellulose, carboxymethyl cellulose, ethylacrylate homopolymers and copolymers, methyl methacrylate homopolymers and copolymers, and the like. Specific examples of alkylated melamine formaldehyde condensation products which may be used in accordance with this invention include propylated methylol-melamine, butylated methylol-melamine, hexylated methylolmelamine, cyclohexylated methylol-melamine, etc. Preferably, the bonding agent constitutes a resin emulsion such as an acrylate emulsion containing at least one reactive pendant group, such as N-methylol acrylamide. Thus, both natural bonding agents, such as albumen and casein, and synthetic bonding agents, such as ethyl cellulose, hydroxyethyl cellulose and urea formaldehyde, can be employed. Prior to the present invention, the choice of the particular bonding agent was extremely critical since the fastness of pigment-dyed fabrics to washing, dry-cleaning, scrubbing and abrasion depended largely upon the type of bonding material employed. In fact, it was not uncommon to employ combinations of two or more types of bonding agents in order to attempt to obtain all of the desired characteristics. The present invention provides a marked improvement in this area in permitting use of a single bonding agent to obtain a greater number of advantages. Based on the percentage of active weight to be deposited on the fabric, between 1 to 20 percent of the bonding agent can be employed, with a preferred amount being in the range of about 4 to percent.

The dispersing agent utilized in the present invention can be of the type normally employed in the art. It is not unknown to employ a material as the dispersing agent which in some formulation may serve as a bonding agent. Such additives may thus be carboxymethyl cellulose, hydroxyethyl cellulose, sodium lignosulfonate, sodium caseinate, or other. Particularly preferred is sodium alginate as the dispersing agent. The sodium alginate is typically added to the other ingredients as a dispersion of the sodium alginate in liquid such that, based on the percent of active weight to be deposited on the fabric, an effective amount between 0.025 and 2 percent of sodium alginate is employed, with the preferred amount being in the vicinity of 0.07 to 1.0 percent. Since the preferred dispersion system is an aqueous system, normally a dispersion of sodium alginate in water is added to the homogeneous aqueous dispersion of pigment and bonding agent.

In order to regulate the pH in a range to or greater than 8, aqueous ammonia is normally employed. However, any amine which can be volatilized at moderate temperatures can be employed. Such amines include ethylamine and isopropylamine.

Textile materials such as cotton fabrics, Dacron-cotton fabrics, polyester fabrics, rayon blends, nylon, Orlon, and similar textile materials are normally treated by running the textile material through a padding bath maintained at a temperature between about 65F. and 180F. Pickup of the padding composition is controlled by regulating the pressure of squeeze rolls to yield the desired wet pickup, e.g. about percent of the weight of the dry fabric being treated. Normally an adequate cure time for the treated fabric is 15 minutes at 325F. Of course, the cure time can be shortened by elevating the temperature. The actual time and temperature used depend on the weight of the fabric and to a lesser degree on the depth of shade applied.

While the following examples illustrate the nature of the present invention, the invention is not intended to be limited to these specific embodiments.

EXAMPLE I A dye composition of the following materials was prepared containing approximately 8.318 percent active weight of materials diluted to percent with The above dye composition was padded onto a 65/35 unsized polyester/cotton fabric to deposit an 85 percent wet pickup, based on the weight of the fabric. Thus, 85 percent of the value shown under percent active weight in the above table was deposited on the fabric.

The fabric treated with the dye composition in the manner indicated above was compared to identical fabric similarly treated except for the absence of a fluorinated organic acid compound in the dye composition. It was found that the dyed fabric containing the fluorochemical was (1) dyed more uniformly, (2) that the dye was more durable to laundering, and (3) that the dyed fabric showed improved soil repellency and soil release characteristics.

A photoelectric reflection meter having a green tristimulus filter was employed to measure the percent reflectance of padded swatches to reveal the durability and soil release characteristics of both the control dye composition and the dye composition containing fluorinated organic acid compounds in accordance with the present invention. In each instance, the padded swatches were cured in a gravity feed circulating hot air oven at 325F. for 15 minutes and then allowed to equilibriate for 24 hours at 50 percent relative humidity at a temperature of 73F. before testing commenced. Soiling of the padded swatches was made with the synthetic soil described in the article by J. M. Salsbury et al. entitled Soil Resistant Treatment of Fabrics in The American Dyestujj Reporter for Mar. 26, 1956. Laundering of soiled fabric swatches was done as described in AATCC Test Method 61, No. IllA, except that 0.2 percent Tide was employed and no sodium metasilicate was employed.

A 62 percent reflectance was obtained from both the control padded swatch and the padded swatch containing the fluorinated organic acid compounds of the present invention. However, following one soiling and then washing by AATCC Test Method 61, No. IIIA, equivalent to five commercial washes, the reflectance of the control padded swatch fell to 44 percent, whereas, after one soiling and washing by AATCC Test Method 61, No. 111A, the padded swatches prepared using the fluorinated organic acid compounds of the present invention had a reflectance value of 61 percent. Even after repeating the soiling and washing procedure on the padded swatches prepared in accordance with the present invention the reflectance value was 58 percent.

EXAMPLE II A qualitative, visual analysis of the difference between padded, dyed fabric swatches containing no fluorinated organic acid compound and padded, dyed fabric swatches containing the fluorinated organic acid compound of the present invention can be clearly shown. For example, employing the composition of Example l, except using benzidine yellow as the pigment, the following results were obtained:

One Soiling Two Soilings One wash & Two Dye No Soil,

Cycle Wash Cycles Composition No Wash Control Yellow, with Dirty Yellow Olive white Green striations With fluoro- Bright uni- Bright Yellow Bright chemical form yellow Yellow EXAMPLE 111 Following the procedure of Example I, a commercially available fluorochemical, representative of the types employed to impart oil and water repellency characteristics to textiles, was incorporated as the fluorochemical in the dye composition. This commercially available material is an aqueous emulsion blend of an aqueous emulsion copolymer whose major component (about 90 percent) is derived from the monomer copolymerized with a minor amount of a hydrocarbon monomer; and an aqueous emulsion hornopolymer derived from 2-ethylhexylacrylate. The proportions of these materials are in the order of about 4 percent copolymer and 9 percent hornopolymer in the blended aqueous emulsion system.

This fluorochemical composition was substituted on the basis of fluorochemical content for the perfluoroctanoyl glycine of Example I in the dye composition otherwise similar to that according to Example I and thereafter applied and tested as in Example I. The pad dyed swatches had and uneven and blotchy appearance of the applied dye and were lacking in fastness properties during laundering. Soil release properties likewise were unsatisfactory.

From the foregoing it will be seen that this invention is well adapted to obtain all of the ends and objects hereinabove set forth, together with other advantages which are obvious and which are inherent to the system. When the fluorinated acid compounds of the formula wherein each R is independently selected from H or an alkyl radical of one to eight carbon atoms and n is an integer of 6 to 18, are added to a dispersion of pigment, bonding agent and dispersing agent the appearance of dyed textile is not only improved, but also the fastness properties of the dye imparted to the textile material is improved thus rendering the dye more durable to laundering. Moreover, the compositions of the present invention also render treated fabrics more soil repellent.

If desired, known anti-soiling substances, such as aluminum silicate; preservatives, such as sodium benzoate or potassium sorbate; water-proofing agents, such as methylol stearamide and methylene-bis-stearamide; anti-static agents; heat stability additives; buffering agents, such as diarnmonium phosphate; etc. may be incorporated into the formulations of the present invention.

Obviously, many modifications and variations of the invention as hereinbefore set forth may be made without departing from the spirit and scope thereof and therefore, only such limitations should be imposed as are indicated in the appended claims.

What is claimed is:

1. A pad dyeing composition comprising a fluorinated organic acid compound and a dispersion of a pigment, bonding agent and dispersing agent said organic acid compound having the formula:

C,,F CONRCHRCOOH wherein each R is independently selected from H or an alkyl radical of one to eight carbon atoms and n is an integer of 6 to 18.

2. The composition of claim 1 wherein the dispersing agent is sodium alginate.

3. The composition of claim 2 wherein the sodium alginate is present in an effective amount, but not more than about two percent by weight.

4. The composition of claim 1 wherein the fluorinated organic acid compound is present in an amount from about 0.1 to about 5 percent by weight.

5. The composition of claim 1 wherein the pigment is present in an amount from about 0.1 to about 10 percent by weight.

6. The composition of claim 1 wherein the bonding agent is present in an amount from about 1 to about 20 percent by weight.

7. The composition of claim 1 wherein the fluorinated organic acid compound is perfluorooctanoyl glycine.

8. A method of making a pad dyeing composition comprising adding a bonding agent to a dispersion of pigment and stirring the bonding agent and pigment until a homogeneous mixture is obtained, adding dispersing agent to the homogeneous mixture of bonding agent and pigment, adjusting the mixture to a pH of at least 8, and adding a fluorinated organic acid compound to the resulting mixture, said organic acid compound having the formula:

wherein each R is independently selected from H or an alkyl radical of one to eight carbon atoms and n is an integer of 6 to 18.

9. The method of claim 8 wherein the composition containing the fluorinated organic acid compound is stirred until a homogeneous mixture is obtained.

10. The method of claim 8 wherein the fluorinated 

1. A pad dyeing composition comprising a fluorinated organic acid compound and a dispersion of a pigment, bonding agent and dispersing agent said organic acid compound having the formula: CnF2n 1 CONRCHRCOOH wherein each R is independently selected from H or an alkyl radical of one to eight carbon atoms and n is an integer of 6 to
 18. 2. The composition of claim 1 wherein the dispersing agent is sodium alginate.
 3. The composition of claim 2 wherein the sodium alginate is present in an effective amount, but not more than about two percent by weight.
 4. The composition of claim 1 wherein the fluorinated organic acid compound is present in an amount from about 0.1 to about 5 percent by weight.
 5. The composition of claim 1 wherein the pigment is present in an amount from about 0.1 to about 10 percent by weight.
 6. The composition of claim 1 wherein the bonding agent is present in an amount from about 1 to about 20 percent by weight.
 7. The composition of claim 1 wherein the fluorinated organic acid compound is perfluorooctanoyl glycine.
 8. A method of making a pad dyeing composition comprising adding a bonding agent to a dispersion of pigment and stirring the bonding agent and pigment until a homogeneous mixture is obtained, adding dispersing agent to the homogeneous mixture of bonding agent and pigment, adjusting the mixture to a pH of at least 8, and adding a fluorinated organic acid compound to the resulting mixture, said organic acid compound having the formula: CnF2n 1CONRCHRCOOH wherein each R is independently selected from H or an alkyl radical of one to eight carbon atoms and n is an integer of 6 to
 18. 9. The method of claim 8 wherein the composition containing the fluorinated organic acid compound is stirred until a homogeneous mixture is obtained.
 10. The method of claim 8 wherein the fluorinated organic acid compound is present in an amount between 0.1 and 5 percent by weight.
 11. The method of claim 10 wherein the fluorinated organic acid compound is perfluorooctanoyl glycine.
 12. The method of claim 8 wherein the dye composition is diluted to 100 percent with water. 